Deep Deoxygenation of Biocrudes Utilizing Fluidized Catalytic Cracking Co-Processing with Hydrocarbon Feedstocks

ABSTRACT

A system and method produce hydrocarbons from biomass by fluid catalytic cracking. In one embodiment, the system is a fluid catalytic cracking system. The system includes a riser. The riser contains a catalyst. The system also includes a biological feed comprising biomass-derived liquid for the riser. In addition, the system includes a hydrocarbon feed comprising hydrocarbons for the riser. The biological feed and the hydrocarbons react in the riser in the presence of the catalyst to convert at least a portion of the biological feed and the hydrocarbons to hydrocarbon products. The hydrocarbon products comprise a concentration of oxygen from about 0.005 wt. % to about 6 wt. %.

CROSS-REFERENCE TO RELATED APPLICATIONS

Not applicable.

STATEMENT REGARDING FEDERALLY SPONSORED RESEARCH OR DEVELOPMENT

Not applicable.

BACKGROUND OF THE INVENTION

1. Field of the Invention

This invention relates to the field of hydrocarbon products and morespecifically to processing biomass-derived feedstock with hydrocarbonfeedstock to produce hydrocarbon products by fluidized catalyticcracking.

2. Background of the Invention

Renewable energy sources have been increasingly used in carbon basedfuels to reduce emissions. A variety of such renewable energy sourceshave been explored. One of such renewable energy sources is biomass.Biomass includes organic sources of energy or chemicals that arerenewable. Typical sources of biomass that have been used for fuelinclude trees and other vegetation, agricultural products and wastes,algae and other marine plants, metabolic and urban wastes.

Several conventional processes have been developed for the conversion ofbiomass. Such conventional processes include combustion, feiinentation,gasification, and anaerobic digestion. However, there are drawbacks tosuch conventional processes for the conversion of biomass. For instance,bio-oil is a product of biomass. Drawbacks to the produced bio-oilinclude the bio-oil having high levels of oxygen. Further drawbacksinclude costly and inefficient upgrading of the bio-oil.

Hydroprocessing of bio-oil has been developed to overcome drawbacks toconventional processes. Hydroprocessing includes hydrotreating,hydrocracking, or combinations thereof. Hydroprocessing may removeoxygen as water. Hydroprocessing also has drawbacks. Drawbacks includethat the high oxygen content of bio-oil typically makes hydroprocessingexpensive in light of the large amount of hydrogen involved. Moreover,hydrogenation may be typical and of a non-selective nature. Forinstance, aromatic components present in the bio-oil may also behydrogenated, which may increase hydrogen consumption beyond the levelsused for oxygen removal.

Consequently, there is a need for improved processes for reducing theoxygen content of bio-oil and other liquid products of biomass.

BRIEF SUMMARY OF SOME OF THE PREFERRED EMBODIMENTS

These and other needs in the art are addressed in one embodiment by afluid catalytic cracking system. The fluid catalytic cracking systemincludes a riser. The riser contains a catalyst (i.e., crackingcatalyst). The fluid catalytic cracking system also includes abiological feed comprising a biomass-derived liquid for the riser. Thefluid catalytic cracking system further includes a hydrocarbon feedcomprising hydrocarbons for the riser. The biological feed and thehydrocarbons react in the riser in the presence of the catalyst toconvert at least a portion of the biological feed and at least a portionof the hydrocarbons to hydrocarbon products. The hydrocarbon productscomprise a concentration of oxygen from about 0.005 wt. % to about 6 wt.%.

These and other needs in the art are addressed in another embodiment bya method for producing hydrocarbon products. The method includesintroducing a biological feed to a riser. The method also includesintroducing a hydrocarbon feed comprising hydrocarbons to the riser. Theriser contains a catalyst (i.e., cracking catalyst). The method furtherincludes reacting the hydrocarbon feed and the biological feed in thepresence of the catalyst to convert at least a portion of the biologicalfeed and the hydrocarbons to hydrocarbon products. The hydrocarbonproducts comprise a concentration of oxygen from about 0.005 wt. % toabout 6 wt. %.

The foregoing has outlined rather broadly the features and technicaladvantages of the present invention in order that the detaileddescription of the invention that follows may be better understood.Additional features and advantages of the invention will be describedhereinafter that form the subject of the claims of the invention. Itshould be appreciated by those skilled in the art that the conceptionand the specific embodiments disclosed may be readily utilized as abasis for modifying or designing other embodiments for carrying out thesame purposes of the present invention. It should also be realized bythose skilled in the art that such equivalent embodiments do not departfrom the spirit and scope of the invention as set forth in the appendedclaims.

BRIEF DESCRIPTION OF THE DRAWINGS

For a detailed description of the preferred embodiments of theinvention, reference will now be made to the accompanying drawings inwhich:

FIG. 1 illustrates an embodiment of a fluid catalytic cracking systemhaving a reactor, a riser, a stripper, a fractionator, and aregenerator;

FIG. 2 illustrates an embodiment of a fluid catalytic cracking systemhaving a reactor, a riser, a fractionator, a stripper, a mixer, and aregenerator;

FIG. 3 illustrates an embodiment of the ACE unit process flow diagramfor Example 8;

FIG. 4 illustrates TGA characteristics of the gas oil feed for Example8;

FIG. 5 illustrates TGA characteristics of 10% py oil-in-gas oil emulsionfor Example 8;

FIG. 6 illustrates coke selectivity vs. cracking conversion for gas oiland 10% py oil-in-gas oil for Example 8;

FIG. 7 illustrates gasoline octane number vs. cracking conversion forgas oil and 10% py oil-in-gas oil for Example 8;

FIG. 8 illustrates GC/MS chromatograph of the liquid product of gas oilfor Example 8; and

FIG. 9 illustrates GC/MS chromatograph of 10% pyrolysis oil and 90% gasoil for Example 8.

DETAILED DESCRIPTION OF THE PREFERRED EMBODIMENTS

FIG. 1 illustrates an embodiment of fluid catalytic cracking system 5for converting at least a portion of biological feed 35 and hydrocarbonfeed 40 to hydrocarbon products 45. In embodiments, fluid catalyticcracking system 5 removes oxygen from biological feed 35 in producinghydrocarbon products 45. In embodiments, fluid catalytic cracking system5 provides hydrocarbon products 45 with an oxygen content (i.e.,concentration) from about 0.005 wt. % to about 6 wt. %, alternativelyfrom about 0.005 wt. % to about 2 wt. %, and alternatively from about0.005 wt. % to about 0.05 wt. %, and further alternatively from about0.4 wt. % to about 0.11 wt. %, and alternatively from about 0.005 wt. %to about 0.2 wt. %. In embodiments, fluid catalytic cracking system 5removes a significant part of the oxygen in the form of COx instead ofas water. In embodiments, COx production ranges from about 3.5 wt % toabout 21.0 wt. % yield from biological feed 35, alternatively from about0.1 wt. % to about 3.3 wt. %, and alternatively from about 0.0 wt. % toabout 3.3 wt. %. Fluid catalytic cracking system 5 also provides asurprising yield of the hydrocarbons in biological feed 35 into liquidhydrocarbons of C₃ or higher (e.g., in hydrocarbon products 45). Inembodiments, fluid catalytic cracking system 5 has a yield ofhydrocarbons in biological feed 35 and hydrocarbon feed 40 to liquidhydrocarbons of C₃ or higher of from about 80.0 wt. % to about 100.0 wt.%, alternatively from about 80.0 wt. % to about 99.0 wt. %, andalternatively from about 80 wt. % to about 95 wt. %. Fluid catalyticcracking system 5 has a coke production of from about 0.6 wt. % to about4.1 wt. %, alternatively from about 2.7 wt. % to about 4.1 wt. %, andalternatively from about 3.1 wt. % to about 4.1 wt. %, and furtheralternatively from about 2.0 wt. % to about 3.4 wt. %, and alternativelyfrom about 2.7 wt. % to about 3.4 wt. %, further alternatively fromabout 2.5 wt. % to about 7.7 wt. %. Without limitation, at a constantconversion, coke yields may increase or decrease depending on thebiological feed 35 used. In embodiments, biological feeds 35 comprisingacidulated vegetable oil and/or palm fatty acid distillate decreasedcoke production at constant conversion by about 15 wt. % to about 25 wt.% as compared to hydrocarbon feed 40 only. In an embodiment, suchbiological feed 35 is used as 20 wt. % of a mixture (i.e., riser feed80) with hydrocarbon feed 40. In some embodiments, biological feed 35comprising sugar derivatives (i.e., ethyl levulinate and/or methylglucoside) increased coke production at constant conversion by about 15wt. % to about 27 wt. %. In an embodiment, such biological feed 35 isused as 20 wt. % of a mixture (i.e., riser feed 80) with hydrocarbonfeed 40. Without limitation, fluid catalytic cracking system 5 providesreactions that break (i.e., crack) high-boiling hydrocarbons intoshorter molecules.

Biological feed 35 includes any suitable type of biomass-derived liquidthat may be converted to a fuel. In embodiments, the biomass-derivedliquid includes liquid derived from biomass. Biomass includes anyorganic source of energy or chemicals that is renewable. Withoutlimitation, examples of biological feed 35 include animal fats, plantfats, triglycerides, biological waste, algae, pyrolysis oil (i.e.,bio-oil), and the like. In an embodiment, biological feed 35 comprisespyrolysis oil.

Hydrocarbon feed 40 includes any conventional fluid catalytic crackingfeed such as heavy hydrocarbon streams. In an embodiment, heavyhydrocarbon streams include high boiling fractions of crude oil,residual oils, or any combinations thereof. High boiling fractions ofcrude oil include atmospheric and vacuum gas oil such as light vacuumgas oil and heavy vacuum gas oil. In some embodiments, high boilingfractions of crude oil may or may not be subjected to hydrotreatmentprior to introduction to riser 15. In embodiments, residual oils includecrude oil atmospheric distillation column residues (e.g., that boilabove 343° C.), crude oil vacuum distillation column residues (e.g.,that boil above 566° C.), tars, bitumen, coal oils, shale oils,Fischer-Tropsch wax, or any combinations thereof. In some embodiments,hydrocarbon feed 40 includes between about 60 volume % and about 100volume % of hydrocarbons boiling at greater than a representative cutofftemperature of a crude oil atmospheric column residue, alternativelybetween about 60 volume % and about 95 volume % of hydrocarbons boilingat greater than a representative cutoff temperature of a crude oilatmospheric column residue, and alternatively between about 90 volume %and about 100 volume % of hydrocarbons boiling at greater than arepresentative cutoff temperature of a crude oil atmospheric columnresidue, and further alternatively between about 95 volume % and about100 volume % of hydrocarbons boiling at greater than a representativecutoff temperature of a crude oil atmospheric column residue. Therepresentative cutoff temperature may be any suitable temperature. In anembodiment, the representative cutoff temperature is 343° C.

In embodiments as shown in FIG. 1, fluid catalytic cracking system 5 hasreactor 10, riser 15 and regenerator 20. It is to be understood thatfluid catalytic cracking system 5 is not limited to the configuration ofthe embodiments shown in FIG. 1. Fluid catalytic cracking system 5 mayinclude any fluid catalytic cracking process that vaporizes and breakshigh-boiling hydrocarbon liquids in biological feed 35 and hydrocarbonfeed 40 into shorter molecules in the presence, at suitable conditions,of a fluid catalytic cracking catalyst (i.e., by contact with thecatalyst). In alternative embodiments (not shown), fluid catalyticcracking system 5 has a stacked reactor, which embodiment of a reactorhas reactor 10 and regenerator 20 in a single vessel with reactor 10disposed above regenerator 20.

In embodiments as shown in FIG. 1, reactor 10 is a reaction vessel.Reactor 10 may include any configuration suitable for fluid catalyticcracking. In embodiments as shown, reactor 10 includes a disengagementdevice suitable for removing catalyst particles from the producthydrocarbon stream, hydrocarbon products 45. In an embodiment, reactor10 includes a cyclone separator unit. In some ° embodiments, reactor 10includes more than one cyclone separator unit. In an embodiment, reactor10 includes stripper 30. In embodiments, stripper 30 is a vessel inwhich residual hydrocarbon products 45 are removed from the spentcatalyst 50.

As shown in FIG. 1, embodiments of fluid catalytic cracking system 5include riser 15. In embodiments, a portion or a majority of thecracking reactions occur in riser 15. In embodiments, the catalyst isdisposed in riser 15. In embodiments, vaporized biological feed 35 andhydrocarbon feed 40 are introduced to riser 15 to facilitatefluidization of the catalyst. It is to be understood that alternativeembodiments include fluidizing the catalyst by any suitable means. Insome embodiments (not shown), fluid catalytic cracking system 5 has morethan one riser 15. Fluid catalytic cracking system 5 may have anyresidence time in riser 15 suitable for catalytic cracking. Embodimentsinclude a residence time from about 0.1 second to about 5 seconds,alternatively from about 0.1 seconds to about 3 seconds, andalternatively from about 0.1 seconds to about 2 seconds, and furtheralternatively from about 0.1 seconds to about 1.5 seconds, andalternatively from about 0.1 seconds to about 1 second, andalternatively from about 0.1 seconds to about 0.5 seconds. Inembodiments, riser 15 may have any individual residence time within theranges disclosed above. Any suitable feed combination may also beprovided to riser 15. In embodiments as shown in FIG. 1, biological feed35 and hydrocarbon feed 40 are fed separately to riser 15, withhydrocarbon feed 40 fed to a bottom portion of riser 15 and biologicalfeed 35 fed to a side of riser 15. Biological feed 35 may be fed at anysuitable location on riser 15, which may include the hydrocarbon feed 40injection point. In embodiments, biological feed 35 is fed proximate tohydrocarbon feed 40. In some embodiments (not illustrated), biologicalfeed 35 and/or hydrocarbon feed 40 may be fed at multiple feed points toriser 15. In an embodiment as shown in FIG. 2, biological feed 35 andhydrocarbon feed 40 are fed to mixer 75. Mixer 75 may be any suitablemixer for mixing biological feed 35 and hydrocarbon feed 40. Inembodiments, mixer 75 provides sonication to biological feed 35 andhydrocarbon feed 40 for agitation. Mixer 75 mixes biological feed 35 andhydrocarbon feed 40 to produce riser feed 80, which comprises biologicalfeed 35 and hydrocarbon feed 40. Without limitation, mixer 75 agitatesbiological feed 35 and hydrocarbon feed 40 to disperse biological feed35.

In embodiments as shown in FIG. 2, riser feed 80 has from about 0.1 wt.% biological feed 35 to about 99.9 wt. % biological feed 35 and fromabout 99.9 wt. % hydrocarbon feed 40 to about 0.1 wt. % hydrocarbon feed40, alternatively from about 1 wt. % biological feed 35 to about 99 wt.% biological feed 35 and from about 99 wt. % hydrocarbon feed 40 toabout 1 wt. % hydrocarbon feed 40, alternatively from about 5 wt. %biological feed 35 to about 95 wt. % biological feed 35 and from about95 wt. % hydrocarbon feed 40 to about 5 wt. % hydrocarbon feed 40, andalternatively from about 20 wt. % biological feed 35 to about 80 wt. %biological feed 35 and from about 80 wt. % hydrocarbon feed 40 to about20 wt. % hydrocarbon feed 40, and further alternatively from about 30wt. % biological feed 35 to about 70 wt. % biological feed 35 and fromabout 70 wt. % hydrocarbon feed 40 to about 30 wt. % hydrocarbon feed40, and alternatively from about 40 wt. % biological feed 35 to about 60wt. % biological feed 35 and from about 60 wt. % hydrocarbon feed 40 toabout 40 wt. % hydrocarbon feed 40. In embodiments, riser feed 80 mayinclude any intermediate amounts of the ranges above of biological feed35 and hydrocarbon feed 40. In the embodiment of FIG. 1, fluid catalyticcracking system 5 includes biological feed 35 and hydrocarbon feed 40introduced to riser 15 with the same ratios of ranges as disclosed forthe embodiment of FIG. 2.

In some embodiments, fluid catalytic cracking system 5 includeshydrotreating hydrocarbon feed 40 prior to introducing hydrocarbon feed40 to riser 15 or to mixer 75. Hydrocarbon feed 40 may be hydrotreatedby any suitable method.

In some embodiments as shown in FIG. 2, an emulsifier 60 may be added.Without limitation, emulsifier 60 facilitates maintaining an emulsion.Emulsifier 60 may include any suitable emulsifier. In embodiments,emulsifier 60 includes polyalkylene oxide block copolymers, non-ionicblock copolymers, ethoxylated alkyl phenols, ethylene oxide propyleneoxide block copolymers, polymerized alcohols and amines, partiallyfluorinated chain hydrocarbons, or any combinations thereof. Commercialexamples of emulsifier 60 include ATLOX® 4912 and ATLOX® 4914. ATLOX® isa registered trademark of Uniqema Americas LLC. Any suitable amount ofemulsifier 60 may be added. In embodiments, emulsifier 60 is added in anamount to provide a riser feed 80 having from about 0.1 wt. % emulsifier60 to about 8 wt. % emulsifier 60, alternatively from about 1 wt. %emulsifier 60 to about 5 wt. % emulsifier 60, and alternatively fromabout 0.1 wt. % emulsifier 60 to about 2.0 wt. % emulsifier,alternatively from about 0.5 wt. % emulsifier 60 to about 1.5 wt. %emulsifier 60. In some embodiments (not illustrated), emulsifier 60 isintroduced to riser 15 in the amounts disclosed above.

Reactor 10 and/or riser 15 may be operated at any suitable temperaturesand pressures to provide the desired cracking. In embodiments, thetemperatures are from about 480° C. to about 630° C., alternatively fromabout 500° C. to about 630° C., alternatively from about 510° C. toabout 600° C., and alternatively from about 510° C. to about 600° C.,and further alternatively from about 500° C. to about 550° C.Embodiments include pressures from about 100 kPa to about 450 kPa,alternatively from about 110 kPa to about 450 kPa, and alternativelyfrom about 110 kPa to about 310 kPa.

The catalyst may include any catalyst or mixture of catalysts suitablefor catalytic cracking whether alone or in combination with catalyticcracking additives. Any suitable catalytic cracking additive may be usedas, without limitation, ZSM-5 additives, gasoline sulfur reductionadditives, SOx reduction additives, or any combinations thereof. In anembodiment, the catalyst is a catalyst mixture of a first catalyst and asecond catalyst. In embodiments, the first catalyst includes anycatalyst suitable for catalytic cracking such as, without limitation, anactive amorphous clay-type catalyst, crystalline molecular sieves, orany combinations thereof. In an embodiment, the crystalline molecularsieve includes zeolites. In embodiments, the zeolites include Xzeolites, Y zeolites, mordenite, faujasite, BETA zeolite, or anycombinations thereof. The crystalline molecular sieve may have anysuitable pore size. In some embodiments, the crystalline molecular sieveis a large pore zeolite with an effective pore diameter from about 0.2nm to about 0.8 nm, alternatively from about 0.5 nm to about 0.8 nm, andalternatively from about 0.7 nm to about 0.74 nm and defined by about 10to about 12 membered rings. Pore size indices are from about 0.6 toabout 38.

In embodiments, the second catalyst includes any catalyst suitable forcatalytic cracking such as zeolites. In embodiments, the zeolitesinclude ZSM-5, ZSM-11, ZSM-12, ZSM-23, ZSM-35, ZSM-38, ZSM-48,ferrierite, erionite, or any combinations thereof. In an embodiment, thezeolites are dispersed on a matrix. The crystalline molecular sieve mayhave any suitable pore size. In some embodiments, the zeolites are smallor medium pore zeolites with an effective pore diameter from about 0.2nm to about 0.7 nm, alternatively from about 0.5 nm to about 0.7 nm anddefined by about 10 or less rings. Pore size indices are from about 0.6to about 30.

In embodiments, the first and/or second catalysts also include activealumina material, binder material, amorphous silica-alumina, phosphates,metal traps, inert filler, or any combinations thereof. Any suitablebinder material may be used such as silica, alumina, or any combinationsthereof. Any suitable inert filler may be used such as kaolin.

In embodiments, the catalysts comprise the following compositions:kaolin from about 10 wt. % to about 60 wt. %, aluminum oxide from about20 wt. % to about 65 wt. %, zeolites from about 5 wt. % to about 60 wt.%, and silicon dioxide from about 2 wt. % to about 30 wt. %; kaolin fromabout 10 wt. % to about 90 wt. %, zeolites from about 5 wt. % to about40 wt. %, and aluminum orthophosphate from about 0.1 wt. % to about 30wt. % or alternatively aluminum orthophosphate from about 0 wt. % toabout 30 wt. %; aluminum oxide from about 0.1 wt. % to about 60 wt. % oralternatively aluminum oxide from about 0 wt. % to about 60 wt. %,silicon dioxide from about 0.1 wt. % to about 10 wt. % or alternativelysilicon dioxide from about 0 wt. % to about 10 wt. %, magnesium oxidefrom about 0.1 wt. % to about 60 wt. % or alternatively magnesium oxidefrom about 0 wt. % to about 60 wt. %, and zinc sulfate from about 0.1wt. % to about 15 wt. % or alternatively zinc sulfate from about 0 wt. %to about 15 wt. %; aluminum oxide from about 10 wt. % to about 40 wt. %,magnesium oxide from about 0.1 wt. % to about 60 wt. % or alternativelymagnesium oxide from about 0 wt. % to about 60 wt. %, and vanadylsulfate from about 0.1 wt. % to about 10 wt. % or alternatively vanadylsulfate from about 0 wt. % to about 10 wt. %; aluminum oxide from about0.1 wt. % to about 40 wt. % or alternatively aluminum oxide from about 0wt. % to about 40 wt. %, silicon dioxide from about 0.1 wt. % to about25 wt. % or alternatively silicon dioxide from about 0 wt. % to about 25wt. %, and magnesium oxide from about 0.1 wt. % to about 40 wt. % oralternatively magnesium oxide from about 0 wt. % to about 40 wt. %; orany combinations thereof. In an embodiment, the catalyst comprises afirst catalyst and a second catalyst with the first catalyst comprisingkaolin from about 10 wt. % to about 50 wt. %, aluminum oxide from about20 wt. % to about 65 wt. %, zeolites from about 5 wt. % to about 60 wt.%, and silicon dioxide from about 2 wt % to about 30 wt. %, and thesecond catalyst comprising aluminum oxide from about 10 wt. % to about40 wt. %, magnesium oxide from about 0 wt. % to about 60 wt. %, andvanadyl sulfate from about 0 wt. % to about 10 wt. %.

The catalyst may have any suitable mixture of first and secondcatalysts. In embodiments, the catalyst has from about 1 wt. % to about30 wt. % second catalyst and from about 99 wt. % to about 70 wt. % firstcatalyst, alternatively from about 10 wt. % to about 25 wt. % secondcatalyst and from about 90 wt. % to about 75 wt. % first catalyst, andalternatively from about 15 wt. % to about 20 wt. % second catalyst toabout 85 wt. % to about 80 wt. % first catalyst. In embodiments, thecatalyst has any intermittent ranges or wt. % of first catalyst andsecond catalyst within the ranges above.

In embodiments as shown in FIGS. 1 and 2, after catalyst enters stripper30, the separated spent catalyst 50 flows to regenerator 20. Regenerator20 operates at any suitable conditions to remove (i.e., burn) a portionor all of the coke accumulated on the spent catalyst 50 (i.e.,regenerate the catalyst). In an embodiment, regenerator 20 operates attemperatures from about 590° C. to about 860° C., alternatively fromabout 590° C. to about 760° C., and alternatively from about 650° C. toabout 860° C., and further alternatively from about 650° C. to about760° C. After such regeneration, regenerated catalyst 55 is returned toriser 15.

In embodiments of operation of fluid catalytic cracking system 5 asshown in FIG. 1, biological feed 35 and hydrocarbon feed 40 areintroduced to riser 15. In some embodiments (not illustrated),emulsifier 60 is also introduced to riser 15. In embodiments ofoperation of fluid catalytic cracking system 5 as shown in FIG. 2,biological feed 35 and hydrocarbon feed 40 are introduced to mixer 75.In some embodiments as shown, emulsifier 60 is also introduced to mixer75. Mixer 75 mixes such components to provide riser feed 80. Thecatalyst disposed in riser 15 is fluidized, and the catalyst, biologicalfeed 35, and hydrocarbon feed 40 (and in some embodiments emulsifier 60)flow upward through riser 15, with biological feed 35 and hydrocarbonfeed 40 contacting the catalyst with the desired cracking reactionsbeing carried out to produce hydrocarbon products 45. The catalyst,biological feed 35, products (i.e., hydrocarbon products 45), andhydrocarbon feed 40 proceed into reactor 10 in which, in someembodiments, cracking reactions continue to occur. Stripper 30 separatesthe catalyst from hydrocarbon products 45. The separated catalyst isintroduced to regenerator 20 as spent catalyst 50, with coke producedfrom the reaction deposited on such spent catalyst 50. In regenerator20, a portion or all of the coke is removed from spent catalyst 50 toproduce regenerated catalyst 55, which is re-introduced to riser 15.Hydrocarbon products 45 exit reactor 10. In some embodiments as shown inFIGS. 1 and 2, hydrocarbon products 45 are introduced to fractionator25. Hydrocarbon products 45 include gasoline, ethylene, propylene,butylene, and the like. Fractionator 25 may include any equipment andprocesses suitable for separating hydrocarbon products 45 into differentfractions. In embodiments, fractionator 25 is a distillation column. Forinstance, in an embodiment, fractionator 25 separates hydrocarbonproducts into light products 65 (i.e., a stream comprising ethyleneand/or propylene) and products 70 (i.e., a stream comprising gasoline).

In some embodiments in which hydrocarbon products 45 comprise water,hydrocarbon products 45 are treated to remove a portion or substantiallyall of the water in hydrocarbon products 45. The water may be removed byany suitable method.

To further illustrate various illustrative embodiments of the presentinvention, the following examples are provided.

Example 1

The catalyst was deactivated using steam deactivation for 20 hours at788° C. with 100 mol % steam. The catalyst was composed of kaolin,aluminum oxide, zeolites, and silicon dioxide. Performance testing tookplace using the Short Contact Time Resid Test Unit, a commerciallyavailable fluidized bed test unit described in available literature(Baas et al., Proc NAM 2008, Houston, of North Am. Cat. Soc.). 20 wt. %of pyrolysis oil (49.7 oxygen wt. %) was blended with a typicaloxygen-free fossil fluid catalytic cracking feed (86.0 wt. % carbon,13.8 wt. % hydrogen, and 0.2 wt. % nitrogen) and stirred at 75° C. in aclosed vessel before injecting into the unit (3 ml of feed). Tests wereperformed at 600° C. with a contact time of 1 second. Liquid product wascollected in a receiver at −6° C. and analyzed. Subsequent analyses wereperformed using standard equipment, all calibrated as subscribed. TableI below shows the product yield distribution as a weight percent of thetotal feed and oxygen amount determined in water-free product fractionobtained with the catalyst at a catalyst to oil ratio (CTO) of 5.5wt/wt.

TABLE I Conversion (wt. %) 68.9 Water 9.0 COx 1.5 Dry gas 0.7 LPG 11.5Gasoline 43.5 LCO 23.1 Bottoms 8.0 Coke 2.7 Oxygen (wt. %) 0.09

Example 2

The catalyst had 80 wt. % of a first catalyst and 20 wt. % of a secondcatalyst. The first catalyst was composed of kaolin, aluminum oxide,zeolites, and silicon dioxide, and the second catalyst was composed ofaluminum oxide, silicon dioxide, magnesium oxide, and zinc sulfate. Thecombined catalysts were deactivated using steam deactivation for 20hours at 788° C. with 100 mol % steam. Performance testing took placeusing the Short Contact Time Resid Test Unit (Baas et al., Proc NAM2008, Houston, of North Am. Cat. Soc.). 20 wt. % of pyrolysis oil (49.7oxygen wt. %) was blended with a typical oxygen-free fossil fluidcatalytic cracking feed (86.0 wt. % carbon, 13.8 wt. % hydrogen, and 0.2wt. % nitrogen) and stirred at 75° C. in a closed vessel beforeinjecting into the unit (3 ml of feed). Tests were performed at 600° C.with a contact time of 1 second. Liquid product was collected in areceiver at −6° C. and analyzed. Subsequent analyses were performedusing standard equipment, all calibrated as subscribed. Table II belowshows the product yield distribution as a weight percent of the totalfeed and oxygen amount determined in water-free product fractionobtained with the catalyst at a CTO of 5.5 wt/wt.

TABLE II Conversion wt. % 62.3 Water 8.6 COx 2.5 Dry gas 0.5 LPG 8.3Gasoline 39.1 LCO 26.3 Bottoms 11.5 Coke 3.2 Oxygen (wt. %) <0.08

Example 3

The catalyst had 80 wt. % of a first catalyst and 20 wt. % of a secondcatalyst. The first catalyst was composed of kaolin, aluminum oxide,zeolites, and silicon dioxide, and the second catalyst was composed ofaluminum oxide, magnesium oxide, and vanadyl sulfate. The combinedcatalysts were deactivated using steam deactivation for 20 hours at 788°C. with 100 mol % steam. Performance testing took place using the ShortContact Time Resid Test Unit (Baas et al., Proc NAM 2008, Houston, ofNorth Am. Cat. Soc.). 20 wt. % of pyrolysis oil (49.7 oxygen wt. %) wasblended with a typical oxygen-free fossil fluid catalytic cracking feed(86.0 wt. % carbon, 13.8 wt. % hydrogen, and 0.2 wt. % nitrogen) andstirred at 75° C. in a closed vessel before injecting into the unit (3ml of feed). Tests were performed at 600° C. with a contact time of 1second. Liquid product was collected in a receiver at −6° C. andanalyzed. Subsequent analyses were performed using standard equipment,all calibrated as subscribed. Table III below shows the product yielddistribution as a weight percent of the total feed and oxygen amountdetermined in water-free product fraction obtained with the catalyst ata CTO of 5.5 wt/wt.

TABLE III Conversion wt. % 64.4 Water 8.1 COx 2.7 Dry gas 0.6 LPG 9.45Gasoline 39.6 LCO 25.0 Bottoms 10.6 Coke 3.9 Oxygen (wt. %) <0.06

Example 4

The catalyst had 80 wt. % of a first catalyst and 20 wt. % of a secondcatalyst. The first catalyst was composed of kaolin, aluminum oxide,zeolites, and silicon dioxide, and the second catalyst was composed ofaluminum oxide, silicon dioxide, and magnesium oxide. The combinedcatalysts were deactivated using steam deactivation for 20 hours at 788°C. with 100 mol % steam. Performance testing took place using the ShortContact Time Resid Test Unit (Baas et al., Proc NAM 2008, Houston, ofNorth Am. Cat. Soc.). 20 wt. % of pyrolysis oil (49.7 oxygen wt. %) wasblended with a typical oxygen-free fossil fluid catalytic cracking feed(86.0 wt. % carbon, 13.8 wt. % hydrogen, and 0.2 wt. % nitrogen) andstirred at 75° C. in a closed vessel before injecting into the unit (3ml of feed). Tests were performed at 600° C. with a contact time of 1second. Liquid product was collected in a receiver at −6° C. andanalyzed. Subsequent analyses were performed using standard equipment,all calibrated as subscribed. Table IV below shows the product yielddistribution as a weight percent of the total feed and oxygen amountdetermined in water-free product fraction obtained with the catalyst ata CTO of 8.5 wt/wt.

TABLE IV Conversion wt. % 69 Water 8.5 COx 2.1 Dry gas 0.7 LPG 12.5Gasoline 40.2 LCO 21.2 Bottoms 10.2 Coke 4.1 Oxygen (wt. %) <0.045

Example 5

The catalyst was composed of kaolin, aluminum oxide, zeolites, andsilicon dioxide. The catalyst was deactivated using steam deactivationfor 20 hours at 788° C. with 100 mol % steam. Performance testing tookplace using the Short Contact Time Resid Test Unit (Baas et al., ProcNAM 2008, Houston, of North Am. Cat. Soc.). 20 wt. % of lignin-richfraction of pyrolysis oil (35.1 oxygen wt. %) was blended with a typicaloxygen-free fossil fluid catalytic cracking feed (86.0 wt. % carbon,13.8 wt. % hydrogen, and 0.2 wt. % nitrogen) and stirred at 75° C. in aclosed vessel before injecting into the unit (3 ml of feed). Tests wereperformed at 600° C. with a contact time of 1 second. Liquid product wascollected in a receiver at −6° C. and analyzed. Subsequent analyses wereperformed using standard equipment, all calibrated as subscribed. TableV below shows the product yield distribution as a weight percent of thetotal feed and oxygen amount determined in water-free product fractionobtained with the catalyst at a CTO of 5.5 wt/wt.

TABLE V Conversion wt. % 69 Water 5.0 COx 0.9 Dry gas 0.7 LPG 12.3Gasoline 46.5 LCO 23.4 Bottoms 7.5 Coke 3.4 Oxygen (wt. %) 0.16

Example 6

The catalyst was composed of kaolin, aluminum oxide, zeolites, andsilicon dioxide. The catalyst was deactivated using steam deactivationfor 20 hours at 788° C. with 100 mol % steam. Performance testing tookplace using the Short Contact Time Resid Test Unit (Baas et al., ProcNAM 2008, Houston, of North Am. Cat. Soc.). 20 wt. % of oxygen-richpyrolysis oil (54.6 oxygen wt. %) was blended with a typical oxygen-freefossil fluid catalytic cracking feed (86.0 wt. % carbon, 13.8 wt. %hydrogen, and 0.2 wt. % nitrogen) and stirred at 75° C. in a closedvessel before injecting into the unit (3 ml of feed). Tests wereperformed at 600° C. with a contact time of 1 second. Liquid product wascollected in a receiver at −6° C. and analyzed. Subsequent analyses wereperformed using standard equipment, all calibrated as subscribed. TableVI below shows the product yield distribution as a weight percent of thetotal feed and oxygen amount determined in water-free product fractionobtained with the catalyst at a CTO of 10.0 wt/wt.

TABLE VI Conversion wt. % 83 Water 13.2 COx 0.3 Dry gas 0.8 LPG 19.8Gasoline 46.5 LCO 13.4 Bottoms 3.6 Coke 2.0 Oxygen (wt. %) 0.017

Example 7 Introduction

This Example estimated the ability of the FCC to process bio-derivedmaterials. The candidate material used in this Example was pyrolysis oil(“py oil”).

SUMMARY

A FCC-reactivity study of bio-materials included py oil. Blends ofvacuum gas oil (VGO) and the bio-materials (py oil) were prepared forlab cracking testing in an Advanced Catalyst Evaluation Unit (ACE ModelR+), based in ACE TECHNOLOGY®, which is a registered trademark of KayserTechnology, Inc.

Laboratory testing of the VGO/pyrolysis oil blend was completed. TheVGO/pyrolysis oil blend run results indicated that the pyrolysis oilappeared to catalytically-crack to useful products (such as gasoline,LCO, and LPG) when tested under typical lab reactor conditions.

Experimental A. Feed and Catalyst

The hydrocarbon feed used both as the “base” feed and as the blendingcomponent for the bio-materials runs was vacuum gas oil. The FCCcatalyst used in this example was an equilibrium catalyst (ECAT).

The FCC reactor runs were VGO-only (“base case”) and 80% VGO/20% py oil(with emulsifier). In all cases, the emulsifier used was ATLOX® 4912.

B. Cracking Reaction/Conditions

All cracking runs were carried out on the ACE FCC reactor. Each blendwas subjected to the following four-run sequence.

TABLE VII Reactor Temperature (° F.) Catalyst/Oil Ratio 995 4.8 995 6.0995 7.5 995 9.0

C. Data Adjustments

Due to the nature of the bio-materials, some adjustments were made tothe ACE data in order to take into account the effects of somenon-standard molecules produced during the reactions. Thus, the productyield and conversion data generated automatically by the ACE equipmentwere adjusted as described below.

The bio-materials contained considerable amounts of oxygen (see TableVIII). Therefore, the catalytic cracking of these materials generatedsome CO, CO₂, and H₂O. Moreover, the bio-materials themselves containsome water-of-processing. On the other hand, the ACE was set up to runonly hydrocarbon feeds, and the product analysis methods were notdesigned to capture and measure species such as CO, CO₂, and H₂O.Therefore, the CO and CO₂ were measured by taking gas samples of thegaseous products evolving from the liquid knockout container in the ACEunit, and having the samples analyzed by an external GC. The resultswere used to adjust the gas analysis produced by the gas GC of the ACEapparatus.

The H₂O content was handled by knowledge of the water content of thebio-material component and by an assumption regarding water-of-reaction.The presence of the emulsifier (1 wt. % ATLOX®) was not taken intoaccount as there was no accurate way to adjust for the reaction productsof that material.

Results and Discussion

Table IX contains summary data of the corrected product yields for theVGO-base case run and the VGO/py oil run. The data collected from theACE unit was analyzed and converted to Constant Conversion, at ConstantCat/Oil Ratio, and at Constant Coke.

In Table IX, it was noted that the liquid yields for the VGO/py oilblend were lower than the corresponding yields for the VGO-only run,which occurred because the water content was normalized over the liquidyields (only). Such normalization was carried out because the water inthe reactor effluent was trapped in the ACE liquid receiver, and wasthus captured as “liquid product weight”, although the ACE'sliquid-analysis GC did not report sample water content. Similarly, thegas/LPG yields were lower for the VGO/py oil blend than for theVGO-only, since the CO and CO₂ were normalized over the gas yields(only).

Note that in addition to the aforementioned adjustments for CO, CO₂, andH₂O, the mass balances for the ACE runs averaged only 97%. Thus, 3% ofthe mass of products from the runs were unaccounted.

The VGO/py oil yields were adjusted to a water-free basis by dividingthe water-included numbers by 0.92 (for liquid yields) and 0.94 (for gasyields). Although water-free basis numbers are not shown in the table,the yields on that basis were close to those of the VGO-only case. Forexample, for the Constant Coke case, the water-free gasoline yield was48.5 wt. %, the LCO yield was 17.3 wt. %, and the slurry yield was 9.9wt. %: numbers comparable to those of the VGO feed.

Tables X, XI, and XII contain more-detailed data than in Table IX, forthe Constant Conversion, Constant Coke, and Constant Cat/Oil ratiocases, respectively. Some of the data in the lower part of these tableswas water-adjusted, as that was how the data was calculated by the ACEdata-processing procedure. In Table X, the calculated cat/oil ratio andthe associated coke-to-cat/oil ratio were not within a normal range andthus were considered to be suspect. Nevertheless, the observationsderived from the data in Tables X-XII were consistent with those derivedfrom Table IX as described above.

TABLE VIII Feed Component Properties Description VGO-Only Feed Py OilFeed API Gravity 22.8 n/a Specific Gravity 60/60° F. n/a Sulfur, wt. %0.118 n/a Total Nitrogen, ppmw 2600 n/d Basic Nitrogen, ppmw 720 n/dWater, wt. % n/a 22.4 Bromine Number n/a Refractive Index @ 20° C.1.4964 n/a Con Carbon Res, wt. % 0.1 n/a Aromaticity by C¹³ NRM, % 21.620 (est.) C—H—N Carbon, wt. % 87.0 55.2 Hydrogen, wt. % 12.0 6.7Nitrogen, wt. % — 0.0 Oxygen, wt. % — 38.1 (dry basis) Metals, ppmw Ni0.10 n/a V 0.4 n/a Fe 1.20 n/a Cu 0.1 n/a Na + K 1.5 n/a Viscosity @100° C., cSt 5.9 n/a Boiling Range D2887/SimDist, 1° F.: (wt. %) 391 IBP584  5 648 10 720 20 772 30 810 40 848 50 890 60 938 70 998 80 1095 901189 95 1328 FBP

TABLE IX Summary Product Yield Data for Lab Cracking Runs ConstantConstant Constant Constant Conversion Constant Coke Constant Cat/OilFeed Conversion 80% VGO Coke 80% VGO Cat/Oil 80% VGO (wt. %) 100% VGO20% Py Oil 100% VGO 20% Py Oil 100% VGO 20% Py Oil Rxn Temp 995 995 995995 995 995 (° F.) Conv., 69.1 69.1 72.8 71.7 72.8 73.2 wt. % C/O, wt/wt4.8 2.5 7.8 5.1 7.7 7.8 Yields: Coke 3.5 4.0 4.7 4.7 4.7 5.4 Hydrogen0.3 0.1 0.2 0.1 0.2 0.1 CO 0.0 0.6 0.0 0.6 0.0 0.6 CO₂ 0.0 0.6 0.0 0.60.0 0.6 Dry Gas 2.2 2.3 2.4 2.4 2.4 2.5 (C1 + C2) Ethylene 0.6 0.7 0.70.7 0.7 0.8 Propane 1.2 1.0 1.3 1.2 1.3 1.3 Propylene 4.3 4.1 4.7 4.34.7 4.5 n-Butane 1.0 0.8 1.1 1.0 1.1 1.0 Isobutane 3.5 3.1 4.2 3.6 4.24.0 C4 Olefins 5.1 5.1 5.1 4.6 5.1 4.7 Gasoline 48.9 44.1 49.5 45.1 49.544.7 (C5-430° F.) LCO (430-650° F.) 19.0 17.2 17.2 16.1 17.2 15.4 HCO(650° F.+) 11.2 10.5 9.4 9.2 9.4 8.5 Water 0.0 6.5 0.0 6.5 0.0 6.5

Mass balances were adjusted for CO, CO₂, and water using someassumptions: gas analysis data was not available for all runs, thusCO/CO₂ ratios were assumed equal for all bio-material runs; gasadjustment ratios were calculated from one run per feed but applied toall bio-material feed cases; liquid adjustment ratios for water werecalculated from one run per feed and applied to all bio-material feedcases; bio-materials were assumed to produce water-of-reaction @ 10relative wt. %; due to inadequacy of assumptions, any final closure ofmass balances was achieved by normalizing data. Conversions were notadjusted for water. Extrapolation was used for the C/O, wt/wt of 2.5because the number was outside of the ACE data.

TABLE X Detailed Product Yield Data at Constant Conversion ACE YieldComparisons at Constant Conversion 80% VGO Feed (wt. %) 100% VGO 20% PyOil Rxn Temp (° F.) 995 995 430° F.+ Conv., wt. % 69.1 69.1 C/O, wt/wt4.8 2.5 Yields, wt. % Coke 3.5 4.0 Hydrogen 0.3 0.1 CO 0.0 0.6 CO₂ 0.00.6 Dry Gas (C1 + C2) 2.2 2.3 Methane 1.0 1.0 Ethane 0.6 0.7 Ethylene0.6 0.7 Propane 1.2 1.0 Propylene 4.3 4.1 n-Butane 1.0 0.8 Isobutane 3.53.1 C₄ Olefins 5.1 5.1 1-butene 1.2 1.1 Isobutylene 1.2 1.1 c-2-butene1.2 1.1 t-2-butene 1.5 1.5 Butadiene 0.1 0.1 Gasoline (C5-430° F.) 48.944.1 LCO (430° F.-650° F.) 19.0 17.2 Slurry (650° F.+) 11.2 10.5 Water0.0 6.5 ** Miscellaneous Yields and 69.9 69.9 Selectivities: 430°F.-Yield, wt. % 69.9 69.9 LPG 15.0 14.8 C₃'s 5.4 5.4 C₄'s 9.6 9.4 C₄Olefins/Total C₄'s 0.5 0.6 Propylene/C₃'s 0.8 0.8 Coke/Cat to Oil 0.71.6 Gasoline (C5-430° F., TBP) Properties RONC by G-CON* 93 93 MONC byG-CON 82 81 Gasoline Composition by G- CON Paraffin, lv % 3 3Isoparaffin, lv % 32 31 Aromatic, lv % 35 34 Naphthene, lv % 10 10Olefin, lv % 20 21 *G-Con is a gasoline compositional analysis modelthat estimates the octane number of the gasoline. ** The following datawere on a water-free basis.

The ACE automated process was not able to measure water in product. Thewater content of the Py Oil was measured to be 22.4 wt. %. Therefore,the contribution to free water in the feed was (22.4 wt. %*20 wt.%=4.5%). Water of reaction was estimated to be 2%, based on 20% feedcontent. Liquid product yields for Py Oil were normalized by a 0.92factor. Gas yields were also corrected for CO and CO₂ via a 0.94 factorfor Py Oil. CO, CO₂ and ratio for all runs were assumed to be constant.Conversions were not adjusted.

TABLE XI Detailed Product Yield Data at Constant Coke ACE YieldComparisons at Constant Coke 80% VGO Feed (wt. %) 100% VGO 20% Py OilRxn Temp (° F.) 995 995 430° F.+ Conv., wt. % 72.8 71.7 C/O, wt/wt 7.75.1 Yields, wt. % Coke 4.7 4.7 Hydrogen 0.2 0.1 CO 0.0 0.6 CO₂ 0.0 0.6Dry Gas (C1 + C2) 2.4 2.4 Methane 1.1 1.0 Ethane 0.7 0.7 Ethylene 0.70.7 Propane 1.3 1.2 Propylene 4.7 4.3 n-Butane 1.1 1.0 Isobutane 4.2 3.6C₄ Olefins 5.1 4.6 1-butene 1.2 1.1 Isobutylene 1.1 1.0 c-2-butene 1.21.1 t-2-butene 1.5 1.4 Butadiene 0.1 0.1 Gasoline (C5-430° F.) 49.5 45.1LCO (430° F.-650° F.) 17.2 16.1 Slurry (650° F.+) 9.4 9.2 Water 0.0 6.5** Miscellaneous Yields and 73.4 72.4 Selectivities: 430° F.-Yield, wt.% 73.4 72.4 LPG 16.5 15.7 C₃'s 6.0 5.9 C₄'s 10.5 9.8 C₄ Olefins/TotalC₄'s 0.5 0.5 Propylene/C₃'s 0.8 0.8 Coke/Cat to Oil 0.6 0.9 Gasoline(C5-430° F., TBP) Properties RONC by G-CON 94 94 MONC by G-CON 83 82Gasoline Composition by G- CON Paraffin, lv % 3 3 Isoparaffin, lv % 3433 Aromatic, lv % 37 36 Naphthene, lv % 9 9 Olefin, lv % 17 19 ** Thefollowing data were on a water-free basis.

The ACE automated process was not able to measure water in product. Thewater content of the Py Oil was measured to be 22.4 wt. %. Therefore,the contribution to free water in the feed was (22.4 wt. %*20 wt.%=4.5%). Water of reaction was estimated to be 2%, based on 20% feedcontent. Liquid product yields for Py Oil were normalized by a 0.92factor. Gas yields were also corrected for CO and CO₂ via a 0.94 factorfor Py Oil. CO, CO₂ and ratio for all runs were assumed to be constant.Conversions were not adjusted.

TABLE XII Detailed Product Yield Data at Constant Cat/Oil Ratio ACEYield Comparisons at Constant Cat/Oil Ratio 80% VGO Feed (wt. %) 100%VGO 20% Py Oil Rxn Temp (° F.) 995 995 430° F.+ Conv., wt. % 72.8 73.2C/O, wt/wt 7.7 7.7 Yields, wt. % Coke 4.7 5.4 Hydrogen 0.2 0.1 CO 0.00.6 CO₂ 0.0 0.6 Dry Gas (C1 + C2) 2.4 2.5 Methane 1.1 1.1 Ethane 0.7 0.7Ethylene 0.7 0.8 Propane 1.3 1.3 Propylene 4.7 4.5 n-Butane 1.1 1.0Isobutane 4.2 4.0 C₄ Olefins 5.1 4.7 1-butene 1.2 1.1 Isobutylene 1.11.0 c-2-butene 1.2 1.1 t-2-butene 1.5 1.4 Butadiene 0.1 0.1 Gasoline(C5-430° F.) 49.5 44.7 LCO (430° F.-650° F.) 17.2 15.4 Slurry (650° F.+)9.4 8.5 Water 0.0 6.5 ** Miscellaneous Yields and 73.4 73.9Selectivities: 430° F.-Yield, wt. % 73.4 73.9 LPG 16.5 16.6 C₃'s 6.0 6.2C₄'s 10.5 10.4 C₄ Olefins/Total C₄'s 0.5 0.5 Propylene/C₃'s 0.8 0.8Coke/Cat to Oil 0.6 0.7 Gasoline (C5-430° F., TBP) Properties RONC byG-CON 94 94 MONC by G-CON 83 83 Gasoline Composition by G- CON Paraffin,lv % 3 3 Isoparaffin, lv % 34 33 Aromatic, lv % 37 37 Naphthene, lv % 99 Olefin, lv % 17 18 ** The following data were on a water-free basis.

TABLE XIII Raw ACE Lab Reactor Data from Cracking Runs ECAT with VGOFeed Normalized ACE Nomialized ACE Normalized ACE Normalized ACE Yields(C/O Yields (C/O Yields (C/O Yields (C/O wt/wt 6.0, Conv. wt/wt 4.8,Conv. wt/wt 7.5, Conv. wt/wt 9.0, Conv. wt. % 71.3) wt. % 68.7) wt. %72.6) wt. % 73.8) Coke 4.1 3.4 4.7 5.2 Gasoline 49.5 48.8 49.3 49.7 LCO17.9 19.2 17.2 16.7 HCO 10.2 11.3 9.5 8.8 H₂ 0.3 0.3 0.2 0.2 C1 1.0 1.01.1 1.1 C2 0.7 0.6 0.7 0.7 C2═ 0.7 0.6 0.7 0.8 C3 1.2 1.1 1.3 1.4 C3═4.5 4.2 4.7 4.8 IC4 3.9 3.5 4.2 4.4 NC4 1.0 0.9 1.1 1.2 C4═ 5.1 5.1 5.25.1 Material Balance 96.6 97.5 97.2 98.4 wt. % Dry Gas wt. % 2.34 2.222.46 2.51 Gasoline RON 93 93 94 94 Gasoline MON 82 82 82 83

TABLE XIV Raw ACE Lab Reactor Data from Cracking Runs ECAT with 80 wt. %VGO and 20 wt. % Py Oil Normalized ACE Normalized ACE Normalized ACENormalized ACE Yields (C/O Yields (C/O Yields (C/O Yields (C/O wt/wt6.0, Conv. wt/wt 4.8, Conv. wt/wt 7.5, Conv. wt/wt 9.0, Conv. wt. %72.2) wt. % 70.0) wt. % 73.3) wt. % 74.1) Coke 5.9 4.0 5.2 5.6 Gasoline48.6 49.0 48.9 49.2 LCO 17.4 18.4 16.8 16.4 HCO 9.8 10.9 9.3 8.8 H₂ 0.10.1 0.1 0.1 C1 1.1 1.1 1.1 1.2 C2 0.7 0.7 0.7 0.7 C2═ 0.8 0.7 0.8 0.9 C31.3 1.2 1.4 1.4 C3═ 4.6 4.4 4.9 4.9 IC4 3.8 3.5 4.3 4.5 NC4 1.0 0.9 1.11.2 C4═ 4.9 5.1 5.2 5.1 Material Balance 97.0 96.3 96.5 98.5 wt. % DryGas wt. % 2.63 2.49 2.68 2.71 Gasoline RON No Data No Data No Data NoData Gasoline MON No Data No Data No Data No Data

In Tables XIII and XIV, the ACE unit conditions included a reactortemperature of 995° F. and a feed tube clearance of 1.125 inches. Thegasoline was a C5 to 430° F. TBP cut, and the LCO was a 430° F. to 650°F. TBP cut. The HCO was a 650° F.+TBP. The test run yields werenormalized to H₂S free.

Example 8 Introduction

The ACE unit, as a versatile tool both for FCC catalysts and feedstockscreening, was used for this example. The ACE unit used was notconfigured to feed two streams simultaneously. To provide a suitablefeed stream for the ACE unit, emulsion was used to disperse pyrolysisoil into gas oil as feed by using an emulsifier.

EXPERIMENTAL Preparation of Emulsion

Proven as an efficient emulsifier, ATLOX® 4912 was used to prepare thepyrolysis oil-in-gas oil emulsion with 10 wt. % of py oil. The gas oilsample was an FCC feed. 1 wt. % of surfactant was used, as the weightratio of gas oil to pyrolysis liquid was fixed at 9:1. The gas oil wasmixed with the surfactant first, followed by addition of pyrolysis oil.The mixture was sonicated at 45° C. for an hour before use.

Catalytic Cracking Condition

For comparison, the gas oil and the emulsion were fed to the ACE unitrespectively, both at four different catalyst/oil ratios. Typicalconditions used in standard FCC catalyst analyses were applied andsummarized in Table XV. The process flow diagram is shown in FIG. 3. Thefeed line temperature was kept at 175° F. to avoid potential coking ordeposition in the feed lines.

RESULTS AND DISCUSSION Feedstock Properties

Pyrolysis oil is well known for its typically poor thermal stability.With excessive coking at high temperature, the feed injection system maybe plugged very easily, especially when the feedline is only 1/16″ OD.Therefore, TGA analysis was conducted prior to feeding of the pyrolysisoil into the reactor to avoid possible plugging in the feed lines. Bothgas oil and the emulsion were tested on the TGA, as shown in FIGS. 4 and5. The major weight loss for both feeds happened in the 300-460° C.region.

For emulsion, the weight loss was 4.8% by 200° C., compared to 0.4% ofthe gas oil. The weight loss of emulsion in the low temperature regionwas mostly attributed to water and volatiles. The VGO began losingweight around 150° C. The peak of the derivative curve was at about 425°C. The emulsion showed two weight loss regions. The first region had apeak at about 115° C., and the weight loss up to 140° C. was about 3.3%.The second weight loss region began shortly after 140° C. with a peakaround 420° C. and was complete by about 470° C. At this mass loss rate,it was not expected to observe significant thermal events, especiallywhen the feed system was kept at a low temperature of only 175° F.

The remaining weights after 500° C. were 0.7 and 2.1 wt % for gas oiland emulsion, respectively. This agrees with the pyrolysis oil havinghigher value of Carbon Residue of around 18.2%.

CHNS analyses, water content, and TAN of the emulsifier, pyrolysis oil,VGO, and the emulsion are shown in Table XVI.

Conversion

Tables XVII-XIX summarize the ACE test results on the basis of constantcatalyst-to-oil ratio, constant coke, and constant conversion. The fulldata set are shown in Tables XIX and XX. The pyrolysis oil appeared tobe very reactive under ACE cracking conditions and easy to crack. At thesame catalyst/oil ratio, the conversion of the 10% emulsion was 1.34%higher than the gas oil (72.93%). Therefore, to reach the same level of430° F.+ conversion, the py-oil-in-gas oil emulsion used a lowercatalyst/oil ratio. For example, at 75% conversion, the py oil blendused a catalyst/oil ratio of 5.76 against 7.11 for gas oil. Or, to reachthe same level of coke yield of 4.5%, the 10% pyrolysis oil emulsion hada lower 430° F.+ conversion.

Under catalytic cracking conditions, pyrolysis oil cracked to formvarious components. At constant catalyst/oil ratio, yields of coke, drygas (C₁ and C₂), C₃'s and C₄'s increased in a statistically significantmanner. The cracking to coke and gas were obtained at the expense ofliquid yields. The yields of gasoline, LCO and HCO declined. Thehydrogen yields decreased as well.

From a visual inspection of the liquid products, it was not obvious thatwater was folioed during the cracking of the pyrolysis oil blend. At thetime of the test, the instrument was not equipped to analyze the CO orCO₂ of the product gas, if any,

Product Distribution

Table XVII shows the yields of both feedstocks under identical catalyticcracking conditions. This provides a good comparison for the crackingperformance of pyrolysis oil against gas oil. For coke and dry gas, thedifference in selectivity was significantly higher for pyrolysis oil.The selectivity was higher for pyrolysis oil in converting into C₃'s andC₄'s, and lower into gasoline and LCO. For hydrogen and HCO, thenegative values indicated pyrolysis oil was not likely selectivelyconverted toward hydrogen and HCO. In turn, the hydrogen and HCOconverted from gas oil were consumed in the catalytic reaction ofpyrolysis oil. The VGO may serve as a hydrogen donor when it was blendedwith pyrolysis oil or pyrolytic lignin for the FCC reaction.

When only as much as 1.2-2.4 grams of samples were used in ACE test,along with the fact that pyrolysis oil was only 10% in the emulsion,experimental error may also have resulted in the negative selectivity inborderline situations.

By comparing coke formation at the same conversion level, as in FIG. 6,the selectivity of coke did not shift significantly for the twofeedstocks, which applied similarly for the gasoline octane number asshown in FIG. 7 even though the GCON detected an improvement in theoctane performance of the gasoline obtained from the pyrolysis blend.The GCON analysis was calibrated based on a conventional FCC gasoline,which may not be completely representative of the pyrolysis oil product.

Oxygenates in Product

To identify the potential oxygenate species in the liquid product fromthe 10% pyrolysis oil-in-gas oil emulsion, GC-MS was used on the liquidproducts, as shown in FIGS. 8 and 9. By comparison of the twochromatograms, no traceable amount of oxygenates were identified withinthe detection limit of the instrument.

Using model oxygenated compounds, reactions on HZSM-5 catalyst attemperatures up to 450° C. were studied, 80° C. below the temperature ofthis example. Alcohols, phenols, aldehydes, ketones, and acids were alltested. Based on these results, even though these oxygenates may differin their reactivities, the product distribution showed similarities asthe reaction included cracking, dehydration, decarboxylation, anddecarbonylation. After the conversion, oxygenates were limited to lowconcentration in the product, if not totally converted.

Oxygenates in the product at FCC conditions would be even lower, sincethere were two mayor differences. The temperature in the ACF test washigher, which promoted the deoxygenation reactions. The catalyst used inthe ACE test was primarily Y zeolite catalyst with a minor amount ofZSM-5 additives. All the acid catalyzed reactions were carried out onthe FCC catalyst. Formation of aromatics from oxygenates were affectedby smaller amount of ZSM-5 catalyst present.

CONCLUSIONS

10 wt % pyrolysis oil-in-gas oil emulsion was successfully catalyticallycracked on an ACE (Advanced Catalyst Evaluation) unit. At FCCconditions, pyrolysis oil was more reactive than gas oil. The yields ofcoke and C₁-C₄ gas were higher, and those of liquid product (gasoline,LCO, HCO) were lower than the respective yields from gas oil. Thereaction results indicated that gas oil may serve as a hydrogen donor inthe FCC processing of pyrolysis oil, which means that hydrogen may notneeded. Low oxygen content was found in the liquid product.

TABLE XV ACE reaction conditions Catalyst Ferndale Refinery ECAT200511008 Catalyst weight 9 grams Feed Injection Rate 1.2 g/minCatalyst/oil ratio 3.75, 5, 6, and 7.5 Fluid-bed reaction 985° F.temperature Feed bottle heater 175° F. Feed-line heater 175° F. Syringeheater 175° F.

TABLE XVI Feed Properties for the ACE Test Pyrolysis ATLOX ® Methods Oil4912 VGO Emulsion H₂O, % D4928 25 0.0492 0.0065 1.91 TAN, mg Modified71.4 7.61 0.38 KOH/g D664 Elemental C 40.46 70.04 86.93 83.87 analysis,% H 7.58 10.66 11.58 11.31 N — — 0.19 — S — — 0.49 0.53 O* 51.96 19.30.81 4.29 *by difference, wet base

TABLE XVII Yields of Gas Oil and 10% py oil-in-gas oil emulsion from ACEtest at constant cat/oil ratio Constant Cat-to-Oil Ratio 10% Py oil +Yield Feedstock 100% gas oil 90% gas oil differences 430° F.+Conversion, 72.93 74.27 1.34 wt. % YIELDS, wt. %: Coke 3.90 4.69 0.79Hydrogen 0.19 0.16 −0.03 Dry Gas (C₁ + C₂) 1.99 2.34 0.35 C₃'s 7.00 7.320.32 C₄'s 11.54 11.93 0.38 Gasoline 48.96 48.27 −0.69 LCO 18.62 18.36−0.25 HCO (670° F.+) 7.80 6.93 −0.87 Gasoline Composition Paraffin, lv %3.0 3.1 0.1 Isoparaffin, lv % 28.6 31.7 3.1 Aromatic, lv % 35.0 29.7−5.3 Naphthene, lv % 9.2 7.8 −1.3 Olefin, lv % 24.2 27.5 3.3 Benzene, lv% 0.9 0.7 −0.1 *: by subtracting the contribution from VGO

TABLE XVIII Yields of Gas Oil and 10% py oil-in-Gas Oil emulsion fromACE test at constant coke yield Constant coke yield 100% Gas 10% Pyoil + Yields Feedstock Oil 90% Gas Oil Differences 430° F.+ Conversion,74.14 73.92 −0.22 wt. % Yields, wt. %: Coke 4.50 4.50 0.00 Hydrogen 0.190.16 −0.03 Dry Gas 2.10 2.31 0.21 (C₁ + C₂) C₃'s 7.16 7.26 0.10 C₄'s11.81 11.84 0.04 Gasoline 49.02 48.30 −0.72 LCO 17.79 18.59 0.80 HCO(670° F.+) 7.44 7.05 −0.40

TABLE XIX Yields of Gas Oil and 10% py oil-in-Gas Oil emulsion from ACEtest at constant conversion Constant Conversion 100% Gas 10% Py oil +Yields Feedstock Oil 90% Gas Oil Differences 430° F.+ Conversion, 75.0075.00 0 wt. % catalyst/oil ratio 7.11 5.76 YIELDS, wt. %: Coke 5.02 5.140.12 Hydrogen 0.18 0.16 −0.02 Dry Gas (C₁ + C₂) 2.18 2.41 0.23 C₃'s 7.287.46 0.18 C₄'s 12.05 12.14 0.09 Gasoline 48.90 48.12 −0.78 LCO 17.2017.88 0.68 HCO (670° F.+) 7.19 6.69 −0.50 Total 100.00 100.00

TABLE XX ACE yield comparisons of two feedstocks ACE Yield Comparisonsof two Feedstocks Pyrolysis Gasoil Evaluation Mode Constant Cat-to-OilRatio Constant Conversion Constant Coke Yields Feedstock 100% Gas Oil10% Pyrolysis 100% Gas Oil 10% Pyrolysis 100% Gas Oil 10% Pyrolysis 430°F.+ Conversion, wt. % 72.93 74.27 75.00 75.00 74.14 73.92 FBCUCatalyst/Oil, wt/wt 5.00 5.00 7.11 5.76 6.13 4.68 YIELDS, wt. %: Coke3.90 4.69 5.02 5.14 4.50 4.50 Hydrogen 0.19 0.16 0.18 0.16 0.19 0.16 DryGas (C₁ + C₂) 1.99 2.34 2.18 2.41 2.10 2.31 Methane 0.76 0.86 0.84 0.890.81 0.85 Ethane 0.51 0.60 0.53 0.61 0.52 0.60 Ethylene 0.72 0.88 0.810.91 0.77 0.86 Propane 1.35 1.42 1.50 1.49 1.44 1.39 Propylene 5.65 5.905.78 5.97 5.72 5.87 n-Butane 1.06 1.10 1.16 1.15 1.12 1.08 Isobutane4.65 4.82 5.12 5.03 4.92 4.72 C₄ Olefins 5.83 6.01 5.76 5.96 5.77 6.041-butene 1.28 1.30 1.26 1.29 1.27 1.31 Isobutylene 1.42 1.42 1.36 1.391.37 1.45 c-2-butene 1.33 1.39 1.34 1.40 1.33 1.39 t-2-butene 1.72 1.791.71 1.79 1.71 1.79 Butadiene 0.09 0.10 0.09 0.10 0.09 0.10 Gasoline48.96 48.27 48.90 48.12 49.02 48.30 LCO 18.62 18.36 17.20 17.88 17.7918.59 670° F.+ 7.80 6.93 7.19 6.69 7.44 7.05 Total 100.00 100.00 100.00100.00 100.00 100.00 LPG/Gasoline 0.38 0.40 0.40 0.41 0.39 0.40LCO/Slurry 2.39 2.65 2.39 2.67 2.39 2.64 Miscellaneous Yields 73.5974.71 and Selectivities: 430° F.-Yield, wt. % 73.59 74.71 75.61 75.4374.77 74.37 LPG 18.54 19.25 19.32 19.60 18.96 19.10 C3s 7.00 7.32 7.287.46 7.16 7.26 C4s 11.54 11.93 12.05 12.14 11.81 11.84 C4 Olefins/TotalC4s 0.51 0.50 0.48 0.49 0.49 0.51 Propylene/C3s 0.81 0.81 0.79 0.80 0.800.81 Coke/Cat to Oil 0.78 0.94 0.71 0.89 0.73 0.96 Gasoline (C5-430° F.,TBP) Properties RONC by G-CON 95.40 96.13 95.81 96.22 95.64 96.08 MONCby G-CON 82.77 83.32 83.27 83.48 83.07 83.24 Gasoline Composition byG-CON Paraffin, lv % 3.0 3.1 3.0 3.1 3.0 3.2 Isoparaffin, lv % 28.6 31.729.3 31.1 29.0 32.0 Aromatic, lv % 35.0 29.7 34.9 31.7 35.0 28.8Naphthene, lv % 9.2 7.8 8.7 7.8 8.9 7.9 Olefin, lv % 24.2 27.5 24.0 26.324.1 28.1 Benzene, lv % 0.9 0.7 0.9 0.8 0.9 0.7

TABLE XXI ACE Test Results of Feedstock 100% Gas Oil Normalized ACENormalized ACE Normalized ACE Normalized ACE Yields (C/O Yields (C/OYields (C/O Yields (C/O wt/wt 3.75, Conv. wt/wt 5.00, Conv. wt/wt 6.00,Conv. wt/wt 7.50, Conv. wt. 71.40%) wt. % 72.56) wt. % 74.21) wt. %75.25) Coke 3.27 3.87 4.40 5.26 Gasoline 48.53 49.07 48.65 49.05 LCO19.64 18.85 17.84 16.95 HCO 8.26 7.93 7.32 7.20 H₂ 0.21 0.18 0.19 0.18C1 0.71 0.74 0.81 0.85 C2 0.50 0.50 0.54 0.53 C2═ 0.66 0.71 0.78 0.81 C31.25 1.32 1.47 1.50 C3═ 5.60 5.51 5.88 5.72 IC4 4.33 4.56 5.05 5.09 NC40.98 1.03 1.15 1.16 C4═ 6.05 5.72 5.93 5.69 Material Balance 99.97 99.85100.74 98.99 wt. % Dry Gas wt. % 1.87 1.95 2.13 2.19 Gasoline RON 95.195.4 95.7 95.8 Gasoline MON 82.3 82.8 83.1 83.3 (R + M)/2 88.7 89.1 89.489.6

TABLE XXII ACE Test Results of Feedstock 10% Pyrolysis Gas Oil + 90% GasOil Normalized ACE Normalized ACE Normalized ACE Normalized ACE Yields(C/O Yields (C/O Yields (C/O Yields (C/O wt/wt 3.75, Conv. wt/wt 5.00,Conv. wt/wt 6.00, Conv. wt/wt 7.50, Conv. wt. 72.99%) wt. % 74.02) wt. %75.06) wt. % 76.47) Coke 3.96 4.66 5.28 6.18 Gasoline 48.43 48.05 47.9947.53 LCO 19.23 18.43 17.89 16.92 HCO 7.31 7.11 6.62 6.20 H₂ 0.16 0.160.16 0.16 C1 0.81 0.86 0.89 0.96 C2 0.59 0.60 0.61 0.63 C2═ 0.82 0.880.91 0.99 C3 1.30 1.43 1.49 1.62 C3═ 5.78 5.89 5.96 6.14 IC4 4.42 4.845.06 5.45 NC4 1.01 1.11 1.16 1.25 C4═ 6.18 6.00 5.99 5.98 MaterialBalance 96.69 99.60 99.20 100.33 wt. % Dry Gas wt. % 2.22 2.33 2.41 2.57Gasoline RON 95.5 95.8 97.1 96.3 Gasoline MON 82.6 83.1 84.0 83.7 (R +M)/2 89.0 89.5 90.5 90.0

Although the present invention and its advantages have been described indetail, it should be understood that various changes, substitutions andalterations may be made herein without departing from the spirit andscope of the invention as defined by the appended claims.

What is claimed is:
 1. A fluid catalytic cracking system, comprising: ariser, wherein the riser contains a catalyst; a biological feedcomprising a biomass-derived liquid for the riser; a hydrocarbon feedcomprising hydrocarbons for the riser; and wherein the biological feedand the hydrocarbons react in the riser in the presence of the catalystto convert at least a portion of the biological feed and thehydrocarbons to hydrocarbon products, wherein the hydrocarbon productscomprise a concentration of oxygen from about 0.005 wt. % to about 6 wt.%.
 2. The fluid catalytic cracking system of claim 1, wherein thebiological feed and the hydrocarbon feed are mixed to provide a riserfeed, wherein the riser feed is introduced to the riser.
 3. The fluidcatalytic cracking system of claim 2, wherein the riser feed comprisesfrom about 0.1 wt. % biological feed to about 99.9 wt. % biologicalfeed, and from about 99.1 wt. % hydrocarbon feed to about 0.1 wt. %hydrocarbon feed.
 4. The fluid catalytic cracking system of claim 2,wherein the riser feed further comprises an emulsifier.
 5. The fluidcatalytic cracking system of claim 1, wherein the catalyst comprises:kaolin from about 10 wt. % to about 60 wt. %, aluminum oxide from about20 wt. % to about 65 wt. %, zeolites from about 5 wt. % to about 60 wt.%, and silicon dioxide from about 2 wt. % to about 30 wt. %; kaolin fromabout 10 wt. % to about 90 wt. %, zeolites from about 5 wt. % to about40 wt. %, and aluminum orthophosphate from about 0 wt. % to about 30 wt.%; aluminum oxide from about 0 wt. % to about 60 wt. %, silicon dioxidefrom about 0 wt. % to about 10 wt. %, magnesium oxide from about 0 wt. %to about 60 wt. %, and zinc sulfate from about 0 wt. % to about 15 wt.%; aluminum oxide from about 10 wt. % to about 40 wt. %, magnesium oxidefrom about 0 wt. % to about 60 wt. %, and vanadyl sulfate from about 0wt. % to about 10 wt. %; aluminum oxide from about 0 wt. % to about 40wt. %, silicon dioxide from about 0 wt. % to about 25 wt. %, andmagnesium oxide from about 0 wt. % to about 40 wt. %; or anycombinations of catalysts thereof.
 6. The fluid catalytic crackingsystem of claim 1, wherein the catalyst comprises: kaolin from about 10wt. % to about 60 wt. %, aluminum oxide from about 20 wt. % to about 65wt. %, zeolites from about 5 wt. % to about 60 wt. %, and silicondioxide from about 2 wt. % to about 30 wt. %.
 7. The fluid catalyticcracking system of claim 1, wherein the catalyst comprises a firstcatalyst and a second catalyst with the first catalyst comprising kaolinfrom about 10 wt. % to about 60 wt. %, aluminum oxide from about 20 wt.% to about 65 wt. %, zeolites from about 5 wt. % to about 60 wt. %, andsilicon dioxide from about 2 wt. % to about 30 wt. %; and the secondcatalyst comprising aluminum oxide from about 10 wt. % to about 40 wt.%, magnesium oxide from about 0 wt. % to about 60 wt. %, and vanadylsulfate from about 0 wt. % to about 10 wt. %.
 8. The fluid catalyticcracking system of claim 7, wherein the catalyst comprises from about 1wt. % to about 30 wt. % second catalyst and from about 99 wt. % to about70 wt. % first catalyst.
 9. The fluid catalytic cracking system of claim1, wherein the biomass-derived liquid comprises pyrolysis oil, and thehydrocarbon feed comprises vacuum gas oil, residual oils, or anycombinations thereof.
 10. The fluid catalytic cracking system of claim1, wherein the fluid catalytic cracking system has a yield ofhydrocarbons in the biomass-derived liquid and the hydrocarbon feed toliquid hydrocarbons of C₃ or higher from about 80 wt. % to about 100 wt.%.
 11. A method for producing hydrocarbon products, comprising: (A)introducing a biological feed to a riser; (B) introducing a hydrocarbonfeed comprising hydrocarbons to the riser, wherein the riser contains acatalyst; and (C) reacting the hydrocarbon feed and the biological feedin the presence of the catalyst to convert at least a portion of thebiological feed and at least a portion of the hydrocarbons tohydrocarbon products, wherein the hydrocarbon products comprise aconcentration of oxygen from about 0.005 wt. % to about 6 wt. %.
 12. Themethod of claim 11, further comprising mixing the biological feed andthe hydrocarbon feed to provide a riser feed, wherein the riser feed isintroduced to the riser.
 13. The method of claim 12, wherein the riserfeed comprises from about 0.1 wt. % biological feed to about 99.9 wt. %biological feed, and from about 99.9 wt. % hydrocarbon feed to about 0.1wt. % hydrocarbon feed.
 14. The method of claim 12, further comprisingmixing an emulsifier with the biological feed and the hydrocarbon feedto provide the riser feed.
 15. The method of claim 11, wherein thecatalyst comprises: kaolin from about 10 wt. % to about 60 wt. %,aluminum oxide from about 20 wt. % to about 65 wt. %, zeolites fromabout 5 wt. % to about 60 wt. %, and silicon dioxide from about 2 wt. %to about 30 wt. %; kaolin from about 10 wt. % to about 90 wt. %,zeolites from about 5 wt. % to about 40 wt. %, and aluminumorthophosphate from about 0 wt. % to about 30 wt. %; aluminum oxide fromabout 0 wt. % to about 60 wt. %, silicon dioxide from about 0 wt. % toabout 10 wt. %, magnesium oxide from about 0 wt. % to about 60 wt. %,and zinc sulfate from about 0 wt. % to about 15 wt. %; aluminum oxidefrom about 10 wt. % to about 40 wt. %, magnesium oxide from about 0 wt.% to about 60 wt. %, and vanadyl sulfate from about 0 wt. % to about 10wt. %; aluminum oxide from about 0 wt. % to about 40 wt. %, silicondioxide from about 0 wt. % to about 25 wt. %, and magnesium oxide fromabout 0 wt. % to about 40 wt. %; or any combinations of catalyststhereof.
 16. The method of claim 11, wherein the catalyst comprises:kaolin from about 10 wt. % to about 60 wt. %, aluminum oxide from about20 wt. % to about 65 wt. %, zeolites from about 5 wt. % to about 60 wt.%, and silicon dioxide from about 2 wt. % to about 30 wt. %.
 17. Themethod of claim 11, wherein the catalyst comprises a first catalyst anda second catalyst with the first catalyst comprising kaolin from about10 wt. % to about 60 wt. %, aluminum oxide from about 20 wt. % to about65 wt. %, zeolites from about 5 wt. % to about 60 wt. %, and silicondioxide from about 2 wt. % to about 30 wt. %; and the second catalystcomprising aluminum oxide from about 10 wt. % to about 40 wt. %,magnesium oxide from about 0 wt. % to about 60 wt. %, and vanadylsulfate from about 0 wt. % to about 10 wt. %.
 18. The method of claim17, wherein the catalyst comprises from about 1 wt. % to about 30 wt. %second catalyst and from about 99 wt. % to about 70 wt. % firstcatalyst.
 19. The method of claim 11, wherein the biomass-derived liquidcomprises pyrolysis oil, and the hydrocarbon feed comprises vacuum gasoil, residual oils, or any combinations thereof.
 20. The method of claim11, further comprising converting hydrocarbons in the biomass-derivedliquid and the hydrocarbon feed to liquid hydrocarbons of C₃ or higherat a yield from about 80 wt. % to about 100 wt. %.